Catalysis by heteropoly compounds. XII. Absorption properties of 12-tungstophosphoric acid and its salts.
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概要
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The absorption of organic molecules into the bulk of H<SUB>3</SUB>PW<SUB>12</SUB>O<SUB>40</SUB> and its salts was studied. Polar (or basic) molecules, such as alcohols and amines, were readily absorbed into H<SUB>3</SUB>PW<SUB>12</SUB>O<SUB>40</SUB>, but nonpolar hydrocarbons were not absorbed. The absorption depended not only on the polarity but also on the molecular size. The diffusion coefficients of the absorption of C<SUB>1</SUB>–C<SUB>4</SUB> alcohols were of similar magnitudes, and were much smaller than that of the intracrystalline diffusion of methanol in ZSM-5. The amounts of absorbed molecules in H<SUB>3</SUB>PW<SUB>12</SUB>O<SUB>40</SUB> tended to be in discrete values: that is, integral multiples of the number of protons (3, 6, etc.). This fact indicates that these polar molecules are protonated and form stable secondary structures throughout the bulk. It was confirmed in the case of methanol or ethanol that the transition between the states of 6 and 9 molecules/anion took place through the pressure changes. The absorptivity was greatly suppressed by the substitution of Cs<SUP>+</SUP> for more than two H<SUP>+</SUP>, while the Na salts showed an absorptivity similar to that of H<SUB>3</SUB>PW<SUB>12</SUB>O<SUB>40</SUB>.
- 公益社団法人 日本化学会の論文
著者
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Okuhara Toshio
Department Of Applied Chemistry Faculty Of Engineering The University Of Tokyo
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Misono Makoto
Department Of Applied Chemistry Faculty Of Engineering The University Of Tokyo
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Lee Kwan
Department Of Communication Stanford University
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Tatematsu Shin
Department of Synthetic Chemistry, Faculty of Engineering, The University of Tokyo
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